Monoazo dyestuffs and their manufacture



Patented Sept. 19, 1944 MONOAZO DYESTUIFFS AND MANU AGTURE I Adolf-Krebser, Riehen, near Basel, and Werner Bossard and Werner Kuster, Basel, Switzerland, assignors to the firm J. R. Geigy A. G., Basel,

Switzerland No Drawing. Application March '25, 1941, Serial No. 385,192. In Switzerland April 26, 1940 6 Claims. (Cl. 260-198) There is known a large number of monoazo dyestuffs of the general formula m It: 7 v i I SOaH O wherein X means a SO2, SO2NH or' a lkyl group, with unsubstituted or substituted benzene nuclei.

sulfonic acid group is new andsurprising and could not be foreseen.

, The present invention is illustrated by the following examples, the parts being by weight, except where otherwise is stated.

, Example] 38.4 parts of 2 amino 4 acetylamino 4 methy1-diphenyl sulfone-35-sulfonic acid are It has now been found that byintroducing a sulfonic acid group in 3-position of the diazonium compound there are obtained monoazo dyestufis of the general formula OH N=N in which formula'Xhas the above cited meaning and both the benzene nuclei can also be further substituted, these new monoazo dyestuffs being technically very valuable. The latter are prepared by couplingdiazotized Z-aminodiphenyl sulfone-3'-sulfonic acid and their substitution products or diazotized 2 -aminobenzene-l-sulfonic acid-N-phenylamide-3'-sulfonic acid or 2- aminobenzene- 1-sulfonic. acid-N-alkyl-N-phenylamide-3'-sulfonic acid 'with 2 amino-8-hydroxynaphthalene-G-sulfonic acid in an acid medium.

By introducing a second sulfonic acid group into the dyestuif molecule in 3'-position-of the dia'zo component, there are surprisingly obtained new dyestufis of remarkable solubility which advantageously distinguish themselves fromthe known analogous monosulfon'ated dyestuffs.

"The acid wool dyeings do' not only show'a near lyunaltered equalizingpower, but they are gen-= er'al-ly"somewhat bluer' and purer and distinctly Taste r10 light. Such an influence of an external 7 diazotized according to known methods in an 1 aqueous solution. The diazonium compound is combined with an acid suspension, of 24 parts of 2-amino 8 hydroxynaphthalene-6-sulfonic acid. The coupling beginning at once is accelerated by slowly neutralizing the exceeding mineral acid. The dyestufi formation being com-v pleted, the red dyestufi is salted out, filtered and dried. Thus a 'viol'et'powder isobtained which from anacid bath dyes wool of uniform red shades of a very good fastness to, light.

The 2-amino-4-propionylaminoor phenoxyacetyl amino 4 methyl diphenylsulfone- 3-su1fonic acids yield similar dyestufis.

Example 2 31.3 parts of 2-aminodiphenyl sulfone-3'j-sulfonic acid are indirectly diazotized, as shown,

and the diazonium compound is combined with an acid suspension of '24 parts of 2-.amino-8- ,hydroxynaphthalene-6-sulfonic acid. The coupling 'is soon completed by neutralizing ex- 'cess mineral acid in the usual manner.

The dyestufi is salted out, filtered and dried. 'The dyestufi thus obtained, which is a bright red powder. dyes wool from an acid bath'pure, bluish-red shades of excellent fastness to light.

Emample 3 r 4113 parts of 2-amino-5-acetylaminobenzenel-sulfonic r acid-N-ethyl-Nphenylamide-3-sulfonic acid are indirectly diazotized according to known methods. The diazonium compound is added to a suspension acid to Congo-red'of 24 parts of 2-amino-8-hydroxynaphtha1ene-6-su1- fonic acid and then the mineral acid is slowly I neutralized in the usual manner until a weakly Congo-red acidreaction is obtained. The coupling is completed after a short time. Thus one obtains a blue-red dyestuff which, after being filtered and dried, forms a dark red powder and yields when applied on wool from an acid bath uniform bluish-red dyeings which are distinguished by a very good fastness to light.

Dyestuifs'containing instead of the acetyl groupa propionyl radical and instead of the N ethyl group a'homologous groupsuch as the para to X and means a member of the group consisting of H and acylamino and Z means a member of the group consisting of H, CH3, halogen, OCI -IaandOCzHa X means a member of the group consisting of S02, SO2NH and SOz.N.a1kyl, said dyestuffs being red to violet powders, dye- Color of the Color of the Diazo component Coupling component dyestufi acid Wool powder dyeing 4. N111 2-amin0-8-hydroxy-naphtha- Violet Bluish-red.

I lene-fi-sulfonic acid. T

NH.CO.CHa SOaH 5. 17TH; -do Violet rednu Red.

6. lTTHz do Bluish-red--. Bluish-red.

SOaH 7 an, I do--. Darkviolet.- Rea;

; I S03 1 V 8. IIIHQ, .;do. Violet.. Bluish-red-.

. NH.CO.OH3' SOaH 9 "NH, do Dark bluish- Do.

I red.

7 Oz CH3 NHOOCBH 803B 11TH; .do Bluish-red-.- Do.

Instead .of the N-ethyl compoundin No. 5Joff the above table there may also be used the bi-m t y e m und, I Nos. 6-, 8 and 9 the methyl group, can be 'substituted by alkoxy group such as the methoxy, ethoxy group and so on without a strong alteration of the properties of the dyestuifs thus obtained. 1 e

In No. '7 the phenyl' amine radical may also be. substituted qby'a p-bromophenylor a tolylor a suitablexylylamine radical.

What we claim is: n

1. The monoazo dyestuffs having in the free state the following general formula fwiirm' "in one of the positions meta and ing wool from acid bath red to violet shades of excellent fastness; properties; especially very good fastness. to light.

2. The monoazodyestufis having in the free state thefollowing general formula 3. The monoazo dyestuffs having in the free being aviolet powder, dyeing wool from acid bath state the following general formula even red shades of excellent fastness to light.

Y 5. The monoazo dyestufi having in the free state the following formula IITHI OH N=N NH2 S02 I v 80: HO

HOaS

SOaH V l 03H I SOaH l5 ben a bri ht red owder d n 001 from cid wherein Y means a member of the group cong g p yel g w sisting of H and acylamino, subjected to the conto light dition that not more than one Y can be difi'erent monoazo dyestufi having in the free from H, and Z means a member of the group state the following fdrmula consisting of H, CH3, halogen, corn and 002m, \said dyestuffs being red to violet powders, dyeing OOCHa wool from acid loath red to violet shades of excel- H NH.CO.CH;

bath pure bluish-red shades of excellent fastness lent fastness properties, especially very good fast- NH I ness to light.

4. The monoazo dyestufi having in the free 4 state the following formula so 0 I HO being a violet powder, dyeingwool from acid bath m bluish-red shades of excellent fastness properties. p ADOLF KREBSER. 7 803B 7 V Y WERNER BOSSARD WERNER KUSTER. e E3 

